CN102112662B - Thallium and potassium nitrate recovery method and recovery apparatus - Google Patents
Thallium and potassium nitrate recovery method and recovery apparatus Download PDFInfo
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- CN102112662B CN102112662B CN200980129855.1A CN200980129855A CN102112662B CN 102112662 B CN102112662 B CN 102112662B CN 200980129855 A CN200980129855 A CN 200980129855A CN 102112662 B CN102112662 B CN 102112662B
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- thallium
- saltpetre
- aqueous solution
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- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 title claims abstract description 314
- 229910052716 thallium Inorganic materials 0.000 title claims abstract description 237
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 title claims abstract description 215
- 235000010333 potassium nitrate Nutrition 0.000 title claims abstract description 157
- 239000004323 potassium nitrate Substances 0.000 title claims abstract description 157
- 238000011084 recovery Methods 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000007864 aqueous solution Substances 0.000 claims abstract description 123
- WKMKTIVRRLOHAJ-UHFFFAOYSA-N oxygen(2-);thallium(1+) Chemical compound [O-2].[Tl+].[Tl+] WKMKTIVRRLOHAJ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910003438 thallium oxide Inorganic materials 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000013078 crystal Substances 0.000 claims abstract description 13
- 238000000926 separation method Methods 0.000 claims description 39
- 150000003475 thallium Chemical class 0.000 claims description 22
- 238000002425 crystallisation Methods 0.000 claims description 14
- 230000008025 crystallization Effects 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000000909 electrodialysis Methods 0.000 claims description 9
- 239000012528 membrane Substances 0.000 claims description 8
- 238000001223 reverse osmosis Methods 0.000 claims description 7
- -1 potassium halide Chemical class 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 description 25
- 239000002244 precipitate Substances 0.000 description 14
- 238000002441 X-ray diffraction Methods 0.000 description 12
- 238000000634 powder X-ray diffraction Methods 0.000 description 12
- 238000005868 electrolysis reaction Methods 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000012795 verification Methods 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 239000002440 industrial waste Substances 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- 238000011105 stabilization Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 241001122767 Theaceae Species 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000001471 micro-filtration Methods 0.000 description 3
- 239000013081 microcrystal Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- GBECUEIQVRDUKB-UHFFFAOYSA-M thallium monochloride Chemical compound [Tl]Cl GBECUEIQVRDUKB-UHFFFAOYSA-M 0.000 description 2
- BXBMHLIYMZRCNK-UHFFFAOYSA-H thallium(3+);trisulfate Chemical compound [Tl+3].[Tl+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BXBMHLIYMZRCNK-UHFFFAOYSA-H 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000011034 membrane dialysis Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/422—Electrodialysis
- B01D61/423—Electrodialysis comprising multiple electrodialysis steps
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/22—Electrolytic production, recovery or refining of metals by electrolysis of solutions of metals not provided for in groups C25C1/02 - C25C1/20
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/147—Microfiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/422—Electrodialysis
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
- C23G5/02—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
- C23G5/04—Apparatus
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Urology & Nephrology (AREA)
- Health & Medical Sciences (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
A thallium and potassium nitrate recovery method, and a recovery apparatus therefor, which comprises a thallium recovery step, in which thallium-containing potassium nitrate is dissolved in water to produce an aqueous solution, dissolved thallium in this aqueous solution is caused to precipitate as metallic thallium or thallium oxide by passing a direct current through this aqueous solution, and then this metallic thallium or thallium oxide is recovered, and a potassium nitrate recovery step, in which dissolved potassium nitrate in this aqueous solution from which the thallium has been removed is caused to precipitate as crystals by concentrating said aqueous solution, and then this potassium nitrate crystal is recovered. With the present invention, the thallium contained in thallium-containing potassium nitrate can be recovered and effectively utilized, and potassium nitrate can also be recovered and effectively utilized.
Description
Technical field
The present invention relates to recovery method and the retrieving arrangement of thallium and saltpetre, more specifically, relate to preferably when from contain thallium saltpetre, reclaiming and effectively utilizing thallium (Tl) as rare metal, reclaim and effectively utilize saltpetre (KNO
3) time thallium that uses and recovery method and the retrieving arrangement of saltpetre.
The application is applied at right of priority its content in the present disclosure based on advocating at Japanese Patent Application 2008-221212 number of Japanese publication on August 29th, 2008.
Background technology
In recent years, because surging to the protection of global environment consciousness, take the cement making equipment that effectively utilizes industrial waste as main, in the final treatment facility of industrial waste, petroleum chemical plant, various factories etc., also pay much attention to environmental cure.For example, in cement making equipment, in order to remove the volatile components such as chlorine contained in the industrial waste, be provided with the chlorine shunting device.
Yet the chlorine bypass dust from this chlorine shunting device is discharged contains the useful heavy metal classes such as thallium, so in order again to recycle as cement raw material, need to reclaim the useful heavy metal classes such as thallium when removing these chlorine compounds.
As the recovery method of in the past thallium, propose to have following the whole bag of tricks.
(1) method of recovery thallium: in the method, contain the thallium raw material by using the reduction of sulfuric acid and reductive agent to leach, the leach liquor that neutralization and filtering obtain, obtain thallium leach liquor and neutralization precipitation thing, after being dissolved in this neutralization precipitation thing in the hydrochloric acid, add reductive agent, the precipitation that generates is carried out solid-liquid separation, thereby reclaim thallium (patent documentation 1).
(2) method of recovery thallium: in the method, by carrying out Oxidation Leaching to containing the thallium material, and carry out solid-liquid separation, obtain containing thallium liquid, contain in the thallium liquid to this and to add reductive agent and chlorine source and make the precipitation such as thallium chloride, by this thallium chloride of vitriol oil heating for dissolving, obtain thallic sulfate solution, reduce this thallic sulfate solution, thereby reclaim thallium (patent documentation 2).
On the other hand, with regard to the general waste of discharging with regard to the industrial waste of discharging from factory or circulation facility etc. or from general family, in the draining that when these wastes are washed, produces, contain the metals such as thallium, lead, cadmium, chromium, mercury in the draining that produces when perhaps city garbage burning ash, flying dust, plastics burning ash etc. being washed, so need to from draining, remove these heavy metals as far as possible, when purifying water, reclaim the useful heavy metal classes such as thallium.
Therefore, propose to have the following method of from draining, removing metal.
(3) by to the perfectly straight stream electric current of draining, the molten metal that is stored in this draining is separated out with the form of oxide compound, from above-mentioned draining, isolate the method (patent documentation 3) of this metal oxide.
According to this method of removing metal, can effectively remove metal contained in the draining, and can significantly reduce the metal concentration in the draining.Thereby have the water quality that can make draining and be increased to the effect that fully is fit to the state of standard of drainage.
Patent documentation 1: No. 2682733 communique of Japan's special permission
Patent documentation 2: No. 2970095 communique of Japan's special permission
Patent documentation 3: TOHKEMY 2007-117965 communique
Summary of the invention
Yet, as contain the thallium saltpetre in the situation that contain thallium in the saltpetre, in the removal method of the recovery method of in the past thallium and metal, have to reclaim thallium and saltpetre by fully individual other operation, and when reclaiming respectively thallium and saltpetre, there is the problem that becomes too high for the cost that reclaims, is difficult to contain thallium saltpetre and effectively utilizes as resource.
Like this, present situation is as follows: for containing thallium saltpetre, effectively do not utilize as resource all the time, and, almost do not study for the method that is used for effectively utilizing yet, on the basis of considering security, process as waste.The present invention carries out in order to solve above-mentioned problem, its purpose is, recovery method and the retrieving arrangement of a kind of thallium and saltpetre are provided, need not to contain thallium saltpetre processes as waste, reclaim and when effectively utilizing this to contain in the thallium saltpetre contained thallium as rare metal, can also reclaim and effectively utilize this to contain saltpetre contained in the thallium saltpetre.
The present invention provides recovery method and the retrieving arrangement of following thallium and saltpetre in order to solve above-mentioned problem.
Namely, the recovery method of thallium of the present invention and saltpetre, from contain thallium saltpetre, reclaim thallium and saltpetre, it is characterized in that, have: the thallium recovery process, by the described thallium saltpetre that contains is dissolved in the water and forms the aqueous solution, and to the perfectly straight stream electric current of this aqueous solution, the molten thallium that is stored in this aqueous solution is separated out with the form of thallium or thallium oxide, and reclaim this thallium or thallium oxide; And the saltpetre recovery process, by the concentrated aqueous solution of having removed this thallium, the molten saltpetre that is stored in this aqueous solution is separated out with the form of crystallization, and reclaim this potassium nitrate crystal.
In the recovery method of this thallium and saltpetre, by to the perfectly straight stream electric current of the aqueous solution that contains thallium saltpetre, the molten thallium that is stored in this aqueous solution is separated out with the form of thallium or thallium oxide, and reclaim this thallium or thallium oxide.Afterwards, by the concentrated aqueous solution of having removed this thallium, the molten saltpetre that is stored in this aqueous solution is separated out with the form of crystallization, and reclaim this potassium nitrate crystal.
Thus, can effectively reclaim and contain thallium contained in the thallium saltpetre and saltpetre, and can effectively utilize thallium and the saltpetre of this recovery.
Preferably remain and be lower than 7 by dissolving the described hydrogen ion concentration that contains the aqueous solution of thallium saltpetre, the molten thallium that is stored in this aqueous solution is separated out with the form of thallium.
Preferably by in the described aqueous solution that contains thallium saltpetre of dissolving, adding potassium halide, the molten thallium that is stored in this aqueous solution is separated out with the form of thallium oxide.
Preferably carry out described concentrated with any unit more than 1 in heating unit, reverse osmosis membrane, the electrodialysis.
The retrieving arrangement of thallium of the present invention and saltpetre reclaims thallium and saltpetre from contain thallium saltpetre, it is characterized in that possessing: dissolving tank is dissolved in the water the described thallium saltpetre that contains and form the aqueous solution; Electrolyzer by to the perfectly straight stream electric current of the described aqueous solution, makes the molten thallium that is stored in this aqueous solution separate out with the form of thallium or thallium oxide; The 1st Separation and Recovery unit, Separation and Recovery this thallium of separating out or thallium oxide; Separate out the unit, the concentrated aqueous solution of having removed this thallium, and the molten saltpetre that is stored in this aqueous solution is separated out with the form of crystallization; And the 2nd Separation and Recovery unit, this potassium nitrate crystal of Separation and Recovery.
In this retrieving arrangement, the thallium Alkitrate that contains that obtains in the dissolving tank is put in the electrolyzer, in this electrolyzer to the perfectly straight stream electric current of the aqueous solution, thereby the molten thallium that is stored in this aqueous solution is separated out, thallium or the thallium oxide of having been separated out by the 1st Separation and Recovery unit Separation and Recovery with the form of thallium or thallium oxide.
And, concentrate the aqueous solution of having removed this thallium by separating out the unit, thereby the molten saltpetre that is stored in this aqueous solution separated out with the form of crystallization, by the 2nd this potassium nitrate crystal of separating out of Separation and Recovery unit Separation and Recovery.
Thus, can effectively reclaim with simple device and contain thallium contained in the thallium saltpetre and saltpetre, and can effectively utilize thallium and the saltpetre of this recovery.
The preferred described unit of separating out possesses any more than 1 in heating unit, reverse osmosis membrane, the electrodialysis.
Recovery method according to thallium of the present invention and saltpetre, have: the thallium recovery process, be dissolved in the water and form the aqueous solution by containing thallium saltpetre, and to the perfectly straight stream electric current of this aqueous solution, the molten thallium that is stored in this aqueous solution is separated out with the form of thallium or thallium oxide, and reclaim this thallium or thallium oxide; And saltpetre recovery process, by the concentrated aqueous solution of having removed this thallium, the molten saltpetre that is stored in this aqueous solution is separated out with the form of crystallization, and reclaim this potassium nitrate crystal, contain thallium contained in the thallium saltpetre and saltpetre so can effectively reclaim with simple operation.Therefore, can from contain thallium saltpetre, reclaim respectively thallium and saltpetre, and again effectively utilize these.
And, because operation is easy, so also can suppress the cost and the time that are used for recovery thallium and saltpetre lower.
Retrieving arrangement according to thallium of the present invention and saltpetre possesses: dissolving tank is dissolved in the water the described thallium saltpetre that contains and form the aqueous solution; Electrolyzer by to the perfectly straight stream electric current of the described aqueous solution, makes the molten thallium that is stored in this aqueous solution separate out with the form of thallium or thallium oxide; The 1st Separation and Recovery unit, Separation and Recovery this thallium of separating out or thallium oxide; Separate out the unit, the concentrated aqueous solution of having removed this thallium, and the molten saltpetre that is stored in this aqueous solution is separated out with the form of crystallization; And the 2nd Separation and Recovery unit, this potassium nitrate crystal of Separation and Recovery contains thallium contained in the thallium saltpetre and saltpetre so can effectively reclaim with simple device.Therefore, can again effectively utilize thallium and the saltpetre that from contain thallium saltpetre, reclaims.
And, because device is easy, so also can suppress the cost that is used for recovery thallium and saltpetre lower.
Description of drawings
Fig. 1 is the schematic diagram of the retrieving arrangement of the expression thallium of an embodiment of the invention and saltpetre.
Fig. 2 is the figure of powder x-ray diffraction (XRD) figure of the precipitate of expression embodiments of the invention 1.
Fig. 3 is the figure of powder x-ray diffraction (XRD) figure of the crystallite of expression embodiments of the invention 1.
Fig. 4 is the figure of powder x-ray diffraction (XRD) figure of the precipitate of expression embodiments of the invention 3.
Fig. 5 is that expression is based on the figure of the change in concentration of the thallium of energising amount.
Nomenclature
1 dissolving tank
2 high-temperature vapors are supplied with and are used pipe arrangement
3 electrolyzers
4 DC stabilization power supplys
5 solid-liquid separating machines
6 crystallizers
7 high-temperature vapors are supplied with and are used pipe arrangement
8 solid-liquid separating machines
Embodiment
With reference to the accompanying drawings, to being used for implementing the recovery method of thallium of the present invention and saltpetre and the best mode of retrieving arrangement describes.
In addition, the manner is the mode that is specifically described in order to understand the aim of invention better, as long as no specifying, does not then limit the present invention.
Fig. 1 is the schematic diagram of the retrieving arrangement of the expression thallium of an embodiment of the invention and saltpetre, is to reclaim thallium (Tl) and saltpetre (KNO from contain thallium saltpetre
3) the example of device.
The retrieving arrangement of this thallium and saltpetre is made of following: dissolving tank 1 will contain thallium saltpetre and be dissolved in the water and form the aqueous solution; High-temperature vapor is supplied with pipe arrangement 2, supplies with the high-temperature vapor more than 100 ℃ in this water in order to heat the water in this dissolving tank 1; Electrolyzer 3 is stored this aqueous solution, and to the perfectly straight stream electric current of this aqueous solution, thus, the molten thallium that is stored in this aqueous solution is separated out with the form of thallium or thallium oxide; DC stabilization power supply 4 is to the perfectly straight stream electric current of the aqueous solution in this electrolyzer 3; Solid-liquid separating machine (the 1st Separation and Recovery unit) 5, the thallium that Separation and Recovery is separated out from the aqueous solution or thallium oxide; Crystallizer (separating out the unit) 6, the concentrated aqueous solution of having removed this thallium makes the molten saltpetre that is stored in this aqueous solution separate out with the form of crystallization; High-temperature vapor is supplied with pipe arrangement (heating unit) 7, supplies with the high-temperature vapor more than 100 ℃ in this aqueous solution in order to heat the aqueous solution in this crystallizer 6; And solid-liquid separating machine (the 2nd Separation and Recovery unit) 8, the potassium nitrate crystal that Separation and Recovery is separated out from this aqueous solution.
As solid-liquid separating machine 5, as long as can Separation and Recovery metal thallium or thallium oxide, possess microfiltration membrane the is arranged micro-filtration, centrifugal separating device etc. of (MF) such as enumerating.
As crystallizer 6, as long as can be by the concentrated aqueous solution of having removed thallium, the molten saltpetre that is stored in this aqueous solution is separated out with the form of crystallization to be got final product, therefore, supply with also can replace into for concentrated aqueous solution counter with pipe arrangement 7 as the high-temperature vapor of the unit that is used for the heating concentrated aqueous solution and soak into film or electrodialysis.And can also possess simultaneously has these high-temperature vapors to supply with pipe arrangement 7, counter 2 or 3 of soaking in film and the electrodialysis.
As solid-liquid separating machine 8, as long as can Separation and Recovery saltpetre, such as enumerating micro-filtration, centrifugal separating device etc.
Then, according to Fig. 1 the recovery method of thallium of the present invention and saltpetre (below, only be called " recovery method ") is described.
The recovery method of present embodiment has: the thallium recovery process, be dissolved in the water and form the aqueous solution by containing thallium saltpetre, and to the perfectly straight stream electric current of this aqueous solution, the molten thallium that is stored in this aqueous solution is separated out with the form of thallium or thallium oxide, and reclaim this thallium or thallium oxide; And the saltpetre recovery process, by the concentrated aqueous solution of having removed this thallium, the molten saltpetre that is stored in this aqueous solution is separated out with the form of crystallization, and reclaim this potassium nitrate crystal.
Employed in this recovery method " containing thallium saltpetre ", the purity of saltpetre was approximately 97～99.8 quality % in order to contain the nitrate of 0.2～3 quality % thallium in the saltpetre.Form with impurity in this saltpetre contains Na, Pb, Ca, Fe etc.
Then, each operation of this recovery method is elaborated.
[thallium recovery process]
" contain the preparation of thallium Alkitrate "
Drop into the water of predetermined amount in the dissolving tank 1, for example drop into respect to dissolve contain thallium saltpetre be 2 quality doubly～10 quality water doubly, that drops into and stir predetermined amount in this water contains thallium saltpetre, makes this contain thallium saltpetre and is dissolved in the water, and contains the thallium Alkitrate thereby form.
The temperature of this water is preferably 10 ℃～50 ℃ scopes so long as contain the temperature of thallium saltpetre dissolving and get final product.
At this, be because during to the perfectly straight stream electric current of this aqueous solution, it is for making the molten thallium that is stored in this aqueous solution effectively separate out sufficient scope with the form of thallium or thallium oxide such as the input amount of above-mentioned restriction water.
In addition, be because, if the input amount of water be lower than contain thallium saltpetre 2 quality doubly, then might exist saltpetre according to the incomplete situation of dissolving of temperature, and the viscosity of the aqueous solution that obtains uprises, be difficult to after operation carry out pump delivery, so not preferred.On the other hand, if the input amount of water above 10 quality that contain thallium saltpetre doubly, then the quantitative change of the thallium in the aqueous solution and saltpetre is few, and the organic efficiency of thallium and saltpetre reduces, so not preferred.
" contain the electrolysis of thallium Alkitrate "
3 pump delivery contain the thallium Alkitrate from dissolving tank 1 to electrolyzer, by the perfectly straight stream electric current of 4 pairs of aqueous solution of DC stabilization power supply, carry out electrolysis in this electrolyzer 3, and the thallium that is dissolved in this aqueous solution is separated out with the form of thallium or thallium oxide.
At this, during electrolysis, if in the above-mentioned aqueous solution, add the acid such as hydrochloric acid, nitric acid, sulfuric acid, the pH (hydrogen ion concentration) of this aqueous solution remained be lower than 7, preferably remain more than 4 and be lower than 7, the molten thallium that is stored in this aqueous solution is separated out with the form of thallium.
On the other hand, if add the potassium halide such as Repone K in the above-mentioned aqueous solution, the molten thallium that is stored in this aqueous solution is separated out with the form of thallium oxide.
Like this, when electrolysis, by adding any a kind in acid, the potassium halide, the molten thallium that is stored in this aqueous solution is separated out with the arbitrary state in thallium, the thallium oxide.
" solid-liquid separation of thallium "
The aqueous solution of this thallium or thallium oxide pump delivery is arranged in solid-liquid separating machine (the 1st Separation and Recovery unit) 5 with separating out, separation and recovery are separated out from the aqueous solution thallium or thallium oxide.
At this, the purity of the thallium that is recovered is about 97 quality %, and the purity of thallium oxide is about 97 quality %.
[saltpetre recovery process]
" heating of the aqueous solution concentrated, crystallization "
The aqueous solution of removing thallium is put in the crystallizer (separating out the unit) 6, heated this aqueous solution by the high-temperature vapor more than 100 ℃ of supplying with pipe arrangement 7 from the high-temperature vapor supply and make the moisture evaporation, thereby make it concentrate, separate out.
The degree that should concentrate need to be concentrated into and separate out in the above-mentioned aqueous solution till the excessive saltpetre that contains, although the also temperature of the interdependent above-mentioned aqueous solution, preferably approximately is concentrated into 1/2～1/10.
Should concentrate, except heating by high-temperature vapor, can also easily carry out with reverse osmosis membrane or electrodialysis.And, also can carry out simultaneously 2 or 3 in them.
[solid-liquid separation of saltpetre]
The aqueous solution of this saltpetre pump delivery is arranged to solid-liquid separating machine (the 2nd Separation and Recovery unit) 8 with separating out, the saltpetre that separation and recovery are separated out from the aqueous solution.
At this, the purity of the saltpetre that is recovered is about 97 quality %, contains thallium or the thallium oxide of the 0.05 quality % that has an appointment.
The draining of discharging from this solid-liquid separating machine 8 is sent to crystallizer 6 and is reused, but also sometimes discharges to the outside after predetermined draining processes implementing.
As described above, according to the thallium of present embodiment and the recovery method of saltpetre, be dissolved in the water and form the aqueous solution by containing thallium saltpetre, and to the perfectly straight stream electric current of this aqueous solution, make the molten thallium that is stored in this aqueous solution separate out and reclaim with the form of thallium or thallium oxide, afterwards, the concentrated aqueous solution of having removed this thallium, make thus the molten saltpetre that is stored in this aqueous solution separate out and reclaim with the form of crystallization, contain thallium contained in the thallium saltpetre and saltpetre so can reclaim respectively and effectively with simple operation.Therefore, can from contain thallium saltpetre, reclaim respectively thallium and saltpetre, and again these effectively be utilized.
And, owing to can carry out continuously thallium recovery process and saltpetre recovery process, can also suppress the cost and the time that are used for recovery thallium and saltpetre lower.
According to the thallium of present embodiment and the retrieving arrangement of saltpetre, consisted of by following: dissolving tank 1, making contains the thallium Alkitrate; High-temperature vapor is supplied with pipe arrangement 2; Electrolyzer 3 is separated out thallium or thallium oxide from this aqueous solution; DC stabilization power supply 4; Solid-liquid separating machine 5, Separation and Recovery metal thallium or thallium oxide; Crystallizer 6 makes the saltpetre in the aqueous solution separate out with the form of crystallization; High-temperature vapor is supplied with pipe arrangement 7; And solid-liquid separating machine 8, the Separation and Recovery potassium nitrate crystal contains thallium contained in the thallium saltpetre and saltpetre so can effectively reclaim with simple device.Therefore, can again effectively utilize thallium and the saltpetre that from contain thallium saltpetre, reclaims.
And, because apparatus structure is simple, so can also suppress the cost that is used for recovery thallium and saltpetre lower.
Embodiment
Below, enumerate embodiment the recovery method of thallium of the present invention and saltpetre is specifically described, but only otherwise exceed its aim, then can to the present invention any restriction not arranged because of following examples.
" embodiment 1 "
Become 1: 5 mode to contain thallium saltpetre with the mass ratio of water, the thallium saltpetre 1kg that contains that will contain the 7210mg/kg thallium puts in the 5kg water, stirs, and obtains containing the thallium Alkitrate.
Then, by platinum electrode the galvanic current that this contains the logical 500mA of thallium Alkitrate is carried out electrolysis, its result has generated the silver color precipitate.
Then, reclaim this precipitate, (XRD) carries out the discriminating of this precipitate by powder x-ray diffraction, and its results verification is thallium.The powder x-ray diffraction of the precipitate of embodiment shown in Fig. 21 (XRD) figure.
Then, the aqueous solution of removing thallium is put in the crystallizer 6, carried out utilizing in 60 minutes the heating of 100 ℃ of high-temperature vapors, make the moisture evaporation, the volume that is concentrated into this aqueous solution becomes 1/10.Thus, in the aqueous solution, separate out the tea white micro-crystals.
Then, use solid-liquid separating machine 8, the aqueous solution of separating out this crystallite is carried out solid-liquid separation, the crystallite that separation and recovery are separated out from the aqueous solution.
(XRD) carries out the discriminating of this crystallite by powder x-ray diffraction, and its results verification is the good saltpetre of crystallinity.The powder x-ray diffraction of the crystallite of embodiment shown in Fig. 31 (XRD) figure.
Analyze thallium content in this crystallite by IPC-AES, its result as can be known, content is 715mg/kg, compares with the initial thallium saltpetre that contains, thallium content becomes approximately 1/10.
" embodiment 2 "
Become 1: 5 mode to contain thallium saltpetre with the mass ratio of water, the thallium saltpetre 1kg that contains that will contain the 7210mg/kg thallium puts in the 5kg water, stirs, and obtains containing the thallium Alkitrate.
Then, contain in the thallium Alkitrate to this and to add hydrochloric acid, the pH of this aqueous solution is remained 5, by platinum electrode the galvanic current of the logical 500mA of this aqueous solution is carried out electrolysis, its result has generated the silver color precipitate.
Then, reclaim this precipitate, (XRD) carries out the discriminating of this precipitate by powder x-ray diffraction, and its results verification is thallium.
Then, the aqueous solution of removing thallium is put in the crystallizer 6, carried out utilizing in 60 minutes the heating of 100 ℃ of high-temperature vapors, make the moisture evaporation, the volume that is concentrated into this aqueous solution becomes 1/10.Thus, in the aqueous solution, separate out the tea white micro-crystals.
Then, use solid-liquid separating machine 8, the aqueous solution of separating out this crystallite is carried out solid-liquid separation, the crystallite that separation and recovery are separated out from the aqueous solution.
(XRD) carries out the discriminating of this crystallite by powder x-ray diffraction, and its results verification is the good saltpetre of crystallinity.
Analyze thallium content in this crystallite by IPC-AES, its result as can be known, content is 965mg/kg, compares with the initial thallium saltpetre that contains, thallium content is approximately 1/8.
" embodiment 3 "
Become 1: 5 mode to contain thallium saltpetre with the mass ratio of water, the thallium saltpetre 1kg that contains that will contain the 7210mg/kg thallium puts in the 5kg water, stirs, and obtains containing the thallium Alkitrate.
Then, contain the Repone K that adds 50g in the thallium Alkitrate to this, by platinum electrode the galvanic current that this aqueous solution leads to 500mA is carried out electrolysis, its result has generated the brown precipitate.
Then, the aqueous solution that uses 5 pairs of solid-liquid separating machines to comprise this precipitate carries out solid-liquid separation, separates from the aqueous solution and the recovery precipitate.
(XRD) carries out the discriminating of this precipitate by powder x-ray diffraction, and its results verification is thallium oxide.The powder x-ray diffraction of the precipitate of embodiment shown in Fig. 43 (XRD) figure.
Then, the aqueous solution of removing thallium oxide is put in the crystallizer 6, carried out utilizing in 60 minutes the heating of 100 ℃ of high-temperature vapors, make the moisture evaporation, the volume that is concentrated into this aqueous solution becomes 1/10.Thus, in the aqueous solution, separate out the tea white micro-crystals.
Then, use solid-liquid separating machine 8, the aqueous solution of separating out this crystallite is carried out solid-liquid separation, the crystallite that separation and recovery are separated out from the aqueous solution.
(XRD) carries out the discriminating of this crystallite by powder x-ray diffraction, and its results verification is the good saltpetre of crystallinity.
Analyze thallium content in this crystallite by IPC-AES, its result as can be known, content is 755mg/kg, compares with the initial thallium saltpetre that contains, thallium content becomes approximately 1/10.
Fig. 5 is that expression is based on the figure of the change in concentration of the thallium of energising amount (C/L).
Among the figure, A only represents the electrolysis based on energising, do not carry out any operation especially and only carry out electrolysis based on energising, so pH process in time is changed to acidity, and thallium concentration and energising amount in the aqueous solution reduce inversely.
Add potassium hydroxide when B represents to switch on and electrolysis when pH is maintained weakly alkaline, identical with A, thallium concentration and energising amount in the aqueous solution reduce inversely.
Therefore electrolysis when adding Repone K when C represents to switch on, can't see separating out on the electrode, sees the precipitation of dark brown thallium oxide, and identical with A, thallium concentration and energising amount in the aqueous solution reduce inversely.
Like this, in only based on any one situation in energising, interpolation potassium hydroxide, the interpolation Repone K, the thallium concentration in the aqueous solution all reduces along with the increase of energising amount (C/L) as can be known.
Claims (8)
1. the recovery method of a thallium and saltpetre reclaims thallium and saltpetre from contain thallium saltpetre, it is characterized in that having:
The thallium recovery process by the described thallium saltpetre that contains is dissolved in the water and forms the aqueous solution, and to the perfectly straight stream electric current of this aqueous solution, makes the molten thallium that is stored in this aqueous solution separate out with the form of thallium or thallium oxide, and reclaims this thallium or thallium oxide;
The saltpetre recovery process by the concentrated aqueous solution of having removed this thallium, makes the molten saltpetre that is stored in this aqueous solution separate out with the form of crystallization, and reclaims this potassium nitrate crystal.
2. the recovery method of thallium as claimed in claim 1 and saltpetre is characterized in that, remains and is lower than 7 by dissolving the described pH that contains the aqueous solution of thallium saltpetre, and the molten thallium that is stored in this aqueous solution is separated out with the form of thallium.
3. the recovery method of thallium as claimed in claim 1 and saltpetre is characterized in that, by add potassium halide in the described aqueous solution that contains thallium saltpetre of dissolving, the molten thallium that is stored in this aqueous solution is separated out as thallium oxide.
4. the recovery method of thallium as claimed in claim 1 and saltpetre is characterized in that, described concentratedly carry out with any unit more than 1 in heating unit, reverse osmosis membrane, the electrodialysis.
5. the recovery method of thallium as claimed in claim 2 and saltpetre is characterized in that, described concentratedly carry out with any unit more than 1 in heating unit, reverse osmosis membrane, the electrodialysis.
6. the recovery method of thallium as claimed in claim 3 and saltpetre is characterized in that, described concentratedly carry out with any unit more than 1 in heating unit, reverse osmosis membrane, the electrodialysis.
7. the retrieving arrangement of a thallium and saltpetre reclaims thallium and saltpetre from contain thallium saltpetre, it is characterized in that possessing:
Dissolving tank is dissolved in the water the described thallium saltpetre that contains and form the aqueous solution;
Electrolyzer by to the perfectly straight stream electric current of the described aqueous solution, makes the molten thallium that is stored in this aqueous solution separate out with the form of thallium or thallium oxide;
The 1st Separation and Recovery unit, Separation and Recovery this thallium of separating out or thallium oxide;
Separate out the unit, the concentrated aqueous solution of having removed this thallium, and the molten saltpetre that is stored in this aqueous solution is separated out with the form of crystallization; And
The 2nd Separation and Recovery unit, this potassium nitrate crystal of Separation and Recovery.
8. the retrieving arrangement of thallium as claimed in claim 7 and saltpetre, wherein, the described unit of separating out possesses any more than 1 in heating unit, reverse osmosis membrane, the electrodialysis.
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| JP2008221212A JP5293005B2 (en) | 2008-08-29 | 2008-08-29 | Method and apparatus for recovering thallium and potassium nitrate |
| JP2008-221212 | 2008-08-29 | ||
| PCT/JP2009/004216 WO2010023942A1 (en) | 2008-08-29 | 2009-08-28 | Thallium and potassium nitrate recovery method and recovery apparatus |
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| CN105217659B (en) * | 2015-10-28 | 2017-01-11 | 天脊煤化工集团股份有限公司 | Method for producing potassium nitrate and system for method |
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| CN1715204A (en) * | 2005-05-30 | 2006-01-04 | 广州大学 | Treating method for waste water containing thallium |
| CN1780923A (en) * | 2003-03-14 | 2006-05-31 | 奥托昆普技术公司 | Method for removing thallium from a zinc-containing solution |
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| JP3508554B2 (en) | 1998-07-02 | 2004-03-22 | 三菱マテリアル株式会社 | Method for producing high-purity thallium iodide and spherical high-purity thallium iodide |
| JP4446426B2 (en) | 2003-01-30 | 2010-04-07 | 株式会社タクマ | Thallium-containing liquid processing method and processing equipment |
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| CN1780923A (en) * | 2003-03-14 | 2006-05-31 | 奥托昆普技术公司 | Method for removing thallium from a zinc-containing solution |
| CN1715204A (en) * | 2005-05-30 | 2006-01-04 | 广州大学 | Treating method for waste water containing thallium |
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